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Roussin黑盐簇阴离子及其“元件化合物”Roussin红盐簇阴离子,是固氮酶活性中心福州模型I(网兜状原子簇模型)的模型物。本文用闭壳层CNDO/2(S,D方案)法计算了它们的电子结构。根据计算所得的Mulliken重叠集居,电荷密度,分子轨道能量和轨道特征等数据,对成键性质进行了分析,得出如下主要结论:两种簇阴离子骨架电子的非定域性都比较强,桥硫原子S_b在由红盐形成黑盐的电子转移过程中起施主作用,两种簇阴离子中都存在M-M键,强度与M-S_b键相近,其主要贡献都来源于金属的s,p_,d_,轨道与硫原子的s,p_z轨道之间的σ作用,金属d轨道的π作用对整个骨架的成键贡献很小。
Roussin black salt anions and its “component compounds” Roussin red salt anions, is the model of nitrogenase activity center Fuzhou Model I (net-like cluster cluster model). In this paper, the electronic structure of CNDO / 2 (S, D scheme) is calculated. According to the calculated data of Mulliken overlapping population, charge density, molecular orbital energy and orbital characteristics, the bonding properties were analyzed. The main conclusions are as follows: The delocalization of the two anionic clusters is relatively strong, The bridge sulfur atom S_b plays a major role in the electron transfer from the red salt to the black salt. The MM clusters present in both anion clusters with similar intensity to the M-S_b bond. The main contributions are all from the metal s, p_, d_, the orbital of the sulfur atom s, p_z orbit between the role of the metal d orbit π effect on the entire skeleton of the bond contribution is small.